CAS: Expanding Base Metal-Catalyzed MHAT Reactions

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With this award, the Chemical Catalysis Program of the Division of Chemistry is supporting the research of Professor Ryan Shenvi of The Scripps Research Institute. Professor Shenvi and his research team are developing inexpensive, earth-abundant, and stable metal catalysts to add hydrogen to carbon-carbon double bonds. This work is providing sustainable alternatives to precious metal-catalyzed processes that have traditionally been used for this purpose. The Shenvi research group is investigating, simplifying, and adapting these reactions for large-scale implementation. They are also developing tandem processes to form new carbon-nitrogen and carbon-carbon bonds after the initial addition of hydrogen. These studies are providing students in the laboratory with training in catalyst design, reaction development, and complex molecule synthesis. Professor Shenvi is also engaged in outreach activities introducing the scientific method to elementary school students and to undergraduate students involved in the Scripps Summer Undergraduate Research Fellowship Program.Professor Shenvi and his research group have recently developed metal-catalyzed hydrogen atom transfer (MHAT) catalysts that can be used in combination with base metal cross-coupling catalysts as a sustainable approach to hydroelementation. To advance the breadth of these studies, new applications of MHAT catalysis in hydroamination and hydrobenzylation processes are being explored. In addition, a new MHAT catalytic cycle is being developed based on inspiration from hydrogen evolution reaction catalysts where reductive turnover is used to eliminate the challenges associated with the delicate balance of oxidant and reductant required in established MHAT systems. These investigations are advancing new modes of catalysis based on readily available metals, particularly manganese, with the optimal choice of and balance of silane reducing agent and oxidant being examined so as to produce a process that is both economical and efficient. This methodology development has the potential for broad scientific impact by providing a viable Mn-catalyzed alternative to precious metal-catalyzed alkene hydroamination.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.